Single source mixtures of metal siloxides

ABSTRACT

This invention pertains to complex mixtures of the formula M is a metal having a valence of from 2–6, L1 is an anionic ligand and L2 is a siloxide or silyl amide ligand suited for producing stable thin-film metal silicates, v is equal to the valence of the metal, and 0&lt;x&lt;v. The bonding is such that an M—O—Si or an M—N—Si linkage exists, respectively, and the stability for the complex is provided by the organic ligand. The invention also relates to a process for preparing the metal siloxide complexes. 
     Thus, the complexes can be represented by the formulas
 
(R) m M—(O—SiR 1 R 2 R 3 ) n 
 
and
 
(R) m M—[N—(SiR 1 R 2 R 3 ) y (R 4 ) 2- y ] n 
 
wherein M is a metal having a valence of 2–6, m and n are positive integers and m plus n is equal to the valence of the metal M. The R type groups, i.e., R, R 1 , R 2 , R 3 , and R 4  represent an organo ligand.

BACKGROUND OF THE INVENTION

Chemical vapor deposition (CVD) of metal siloxides has been used to deposit stable thin-film silicates as gate dielectrics (high dielectric constant) onto silicon substrates for use in the microelectronics industry. Single source metal siloxide precursors greatly simplify production and processing. Representative single source precursors which have been used in the past include Zr(OSiMe₃)₄, Zr(OSiEt₃)₄, Hf(OSiEt₃)₄, Zr[OSi(OtBu)₃]₄, Hf[OSi(OtBu)₃]₄, (thd)₂Zr(OSiMe₃)₂, and (thd)₂Hf(OSiMe₃)₂.

Chemical vapor deposition of these single source metal siloxides, although simplifying some aspects in the production of thin films introduce different problems to the process and in the design of the thin-film composition. Zr(OSiMe₃)₄, for example, is a solid at room temperature. The compounds (thd)₂Zr(OSiMe₃)₂ and (thd)₂Hf(OSiMe₃)₂ are solids and suffer from low volatility due to the use of bulky thd ligands. Other precursors such as Zr[OSi(OtBu)₃]₄ and Hf[OSi(OtBu)₃]₄ also have been found to have relatively low volatility.

Single source metal siloxide precursors which are liquids such as Zr(OSiEt₃)₄ and Hf(OSiEt₃)₄, are preferred for thin-film applications. Although, in liquid form, they too can present problems when designing the desired composition of the resultant thin-film. The design becomes a problem because each of the previous liquid metal siloxides has a well-designed metal:Si ratio of either 1:4 (0.25) or 1:2 (0.5). For example Zr(OSiMe₃)₄ has a metal:Si ratio of 1:4 and (thd)₂Zr(OSiMe₃)₂ has a metal:Si ratio of 1:2. To achieve thin-film compositional ratios other than that produced from the pure 1:4 and 1:2 complexes, the art has employed the use of multiple sources. One technique employing secondary sources for achieving metal silicon ratios other than the fixed ratios of 1:2 and 1:4. is through the use of mixture of a silicon containing metal (zirconium) source. e.g., Zr(OSiMe₃)₄ and a non-silicon containing metal (zirconium) source, e.g., Zr(OtBu)₄ delivered either separately, as a mixture or dissolved in a solvent. Another technique is through the use of a non-metal containing compound of silicon, e.g., Si(NMe₂)₄ and a metal siloxide compound, e.g., Zr(OSiMe₃)₄ delivered either separately, as a mixture or dissolved in a solvent. Another technique uses a non-metal containing silicon compound, e.g., Si(NMe₂)₄ and a metal containing compound, e.g., Zr(NEt₂)₄ delivered either separately, as a mixture, or dissolved in a solvent.

Single source mixtures of separate complexes introduce a number of problems to the CVD process. Because the relative rate of deposition for each precursor may vary significantly with temperature and pressure due to differences in activation energy, it is difficult to uniformly control the metal:Si ratio deposited as a thin-film dielectric. The use of separate metal and silicon sources also requires delivery equipment for multiple chemical sources as well as control over the ratio in which they are delivered.

Representative patents and articles illustrating the preparation and deposition methods for single source precursors are as follows:

WO 01/25502 discloses gate dielectric films of zirconium and hafnium silicates on silicon substrates. The precursor metal compound includes a metal such as zirconium or hafnium and at least an alkoxide or β-diketonate; a second precursor not containing silicon to provide a ratio M_(x)/Si_(1- x) of from 0.01 to 0.99. These precursors are produced by reacting a β-diketone, such as 2,2,6,6-tetramethyl-3,5-heptanedione (Hthd), with ZrCl₂ suspended in diethyl ether. The resulting compound then are mixed in one to two molar ratio with LiOSiMe₃, thereby forming Zr(thd)₂(OSiMe)₂. Deposition of a mixture of Zr(OSiMe₃)₄ and Zr(OtBu)₄ is shown.

U.S. Pat. No. 6,238,734 discloses the deposition of a metal compound or mixture of at least a two ligand complex onto substrates suited for semiconductor fabrication. A mixture of two or more metal-ligand complexes as the precursor is employed. Ligands are the same and are selected from the group consisting of alkyls, alkoxides, halides, hydrides, amides, imides, azides, nitrates, cyclopentadienyls, carbonyls, and their fluorine, oxygen and nitrogen substituted analogs. Representative metal-ligand complexes include: Si(N(CH₂CH₃)₂), Ti(N(CH₂CH₃)₂)₄, Zr(N(CH₂CH₃)₂)₄, Hf(N(CH₂CH₃)₂)₄, V(N(CH₂CH₃)₂)₅, V(N(CH₂CH₃)₂)₄, Nb(N(CH₂CH₃)₂)₅, Nb(N(CH₂CH₃)₂)₄, CH₃CH₂N═Nb(N(CH₂CH₃)₂)₃, CH₃CH₂N═V(N(CH₂CH₃)₂)₃, (CH₃CH₂N═)₂W(N(CH₂CH₃)₂)₂, (CH₃CH₂N═)₂Mo(N(CH₂CH₃)₂)₂, and CH₃CH₂N═Ta(N(CH₂CH₃)₂)₃.

Terry et al in an article, Trialkoxysiloxy Complexes as Precursors to MO ₂.4SiO ₂(M═Ti, Zr, Hf) Materials, Chem. Mater. 1991, 3 1001–1003 disclose chemical routes to ceramic materials based upon alkoxysiloxy transition-metal complexes as single source precursors to homogenous metal silicate networks. These complexes of the formula M[OSi(OtBu)₃]₄ where M═Ti, Zr, or Hf are used to produce MO₂.4SiO₂ materials. One type of complex is produced by refluxing a toluene solution of HOSi(OtBu)₃(4 equiv) with Ti(NEt₂)₄.

BRIEF SUMMARY OF THE INVENTION

This invention pertains to precursor mixtures of the formula M(L1)_(x)(L2)_(v-x) wherein M is a metal having a valence of from 2–6, L1 is an anionic ligand and L2 is a siloxide or silyl amide ligand suited for producing stable thin-film metal silicates, v is equal to the valence of the metal, and 0<x<v. The bonding is such that an M—O—Si or an M—N—Si linkage exists, respectively. The invention also relates to a process for preparing the metal siloxide and metal silyl amide precursor mixtures.

The complexes forming the mixture are more specifically represented by the formulas: (R)_(m)M—(O—SiR₁R₂R₃)_(n) and (R)_(m)M—[N—(SiR₁R₂R₃)_(y)(R₄)_(2-y)]_(n) wherein M is a metal valence 2–6, m and n are positive integers and m plus n is equal to the valence of the metal M, and y is 1 or 2. The R type groups, i.e., R, R₁, R₂, R3, and R₄ represent an organic ligand. They may be like or unlike.

There are significant advantages to the metal precursor complexes described herein and their application to thin film formation such as in microelectronic circuits.

an ability to formulate metal/siloxane complexes at preselected ratios of M:Si;

an ability to formulate single source precursors for use in deposition processes such as CVD;

an ability to eliminate the processing difficulties associated with physical mixtures of single source precursors; e.g., those difficulties associated with different rates of deposition, different deposition temperatures; and compositional variations; and,

an ability to produce single source precursors having a definite metal:Si ratio which are relatively insensitive to deposition temperature and pressure changes due to the fact the individual complexes of the single source precursor mixture have similar activation energies and, therefore, similar relative rates of deposition at a variety of temperatures.

BRIEF DESCRIPTION OF THE DRAWING

The FIGURE is a graph of concentrations of various identified elements in deposited films as a function of temperature.

DETAILED DESCRIPTION OF THE INVENTION

This invention relates to a single source metal siloxide precursor mixtures of the form M(L1)_(x)(L2)_(v-x) wherein M is a metal having a valence or from 2–6, typically Zr, Ti of Hf when used in microelectronic applications, L1 is an anionic ligand and L2 is a siloxide or silyl amide ligand suited for producing stable thin-film metal silicates, v is equal to the valence of the metal, and 0<x<v., The resultant mixtures contain metal complexes in which an anionic silicon-containing moiety is bound to the metal through an oxygen or nitrogen atom such that a M—O—Si or M—N—Si linkage exists.

As source reagents for metal organic chemical deposition (MOCVD) and the preparation of the precursor, Group 2–6 metals are suited for the synthesis of the metal siloxides and silyl amides. Representative metals and lanthanides include aluminum, gallium, indium, thallium, tin, lead, antimony, bismuth, beryllium, magnesium, calcium, strontium, barium, scandium, yttrium, lanthanum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium ytterbium, lutetium, actinium, thorium, protactinium and uranium. Preferably, the metals employed in the synthesis of metal siloxides and silylamides for microelectronic applications are the Group 4 metals, zirconium, hafnium, and titanium and the Group 5b metals niobium, tantalum and vanadium. For some applications the Group 3 metals aluminum, gallium, indium and thallium are preferred.

Ligands L1 and L2 in the formula M(L1)_(x)(L2)_(v-x) and represented by the R type groups, R, R₁, R₂, R₃, and R₄ in the formulas; (R)_(m)M—(O—SiR₁R₂R₃)_(n) and (R)_(m)M—[N—(SiR₁R₂R₃)_(n)(R₄)_(2-y)]

can be monodentate or polydentate and include C₁₋₈ alkyl, C₁₋₈ alkoxides, benzyl, halides, hydrides, amides, imides, azides, nitrates, cyclopentadienyls, carbonyls, and their fluorine, oxygen and nitrogen substituted analogs, a β-diketonate, and N(R₅)₂ where R₅ is C₁₋₈ alkyl, C₁₋₈ alkoxide, C₁₋₈ dialkylamino and benzyl. As is known the type of R—R₅ groups in a single source metal siloxide precursor have an effect on the properties of the resultant metal siloxide. R groups should be selected to provide the type of properties desired for the deposition process employed. Liquid single source metal siloxide and silyl amide precursors, often use non-bulky groups, e.g., methyl, ethyl and so forth. Crown ethers and β-diketones such as 2,4-pentanedione sometimes referred to herein as hexafluoroacetylacetone and 2,2,6,6-tetramethylheptane-3,5-dione can be used.

Specific examples of C₁₋₈ alkyl include methyl, ethyl, i-propyl and t-butyl; benzyl, the C₁₋₈ alkoxides, e.g., methoxy, ethoxy, propoxy, and i-butoxy, s-butoxy, t-butoxy; ethers such as methyl ether, diethyl ether, phenyl ether and so forth; amides such as formamide, acetamide and benzamide, dimethyl amido, diethyl amido, ethylmethyl amido, butyl amido, dipropyl amido, methylpropyl amido, ethylpropyl amido; and amines such as dimethylamine, diethyl amine. It is important to use the same or common ligands, homoleptic ligands, to avoid potential ligand exchange problems of the prior art.

Metal siloxides are preferred to metal silyl amides due to their greater ease of oxidation and lesser steric bulk. In addition, the preferred metal siloxide precursor complexes are room temperature liquids with sufficiently low viscosity to allow the use of neat liquid source delivery without incorporating solvents or heated source containers or delivery lines prior to vaporization.

The metal siloxide single source complexes are typically but not exclusively derived from the reaction of a metal oxide complex and a silanol including but not limited to silane-diols and -triols. Sometimes these silanols are considered Si analogs of alkoxides. Examples of silane diols and silane triols suited for producing the metal siloxides include: C₁₋₈ alkyl silanols, such as trimethylsilanol, triethyl silanol, tri-i-and n-propyl silanol, and t-butyl silanol.

Silyl amides are similar to siloxides, but incorporate N in place of O. Silyl amides are typically but not exclusively derived from silyl amines including by not limited to disilyl amines such as hexamethyldisilazane (HMDS).

One method for preparing the metal siloxide precursor complex is to react a group 2–6 metal complex of the formula M(OR)_(v) with a silanol of the formula HO—Si(R₁R₂R₃). The metal oxide complex and the silanol or silyl amide may be reacted in various molar ratios leading to various metal to silicon mole ratios, the excess ligands providing the stabilizing influence. Because there is an excess of ligand, the M:Si ratios may vary slightly within a given composition. For purposes of composition design, the composition is assumed to be approximately in proportion to the mole ratio in which they are reacted. Also, because of these differences, the single metal siloxide or metal silylamide species is an intimate mix of metal complexes having preselected M:Si ratios of 1:X where 0<x<v.

A solvent may be used to form the metal siloxides or metal silyl amides. Typically, the silanols or silyl amines employed to form the complex are dissolved in an appropriate solvent to produce crude versions of the aforementioned mixtures. Examples of solvents include: hydrocarbons such as hexane, octane and the like, ethers such as tetrahydrofuran and so forth.

Purification of the reaction product is accomplished by removal of the solvent under vacuum and by distillation. The purified mixture is characterized by NMR spectrometry and GC-MS. The actual compositions of the metal siloxide and metal silylamide complexes may be determined analytically using either NMR, GC-MS or some other equivalent analytical technique. The reaction product will contain detectable quantities of at least two separate complexes with different values of x such that the difference between the individual values of x is 1.

Examples of metal complex mixtures that can be produced by the process include: [(CH₃CH₂)₂N]_(m)Zr[Osi(CH₂CH₃)₃]_(n);, [(CH₃CH₂)₂N]_(m)Hf[OSi(CH₂CH₃)₃]_(n), [(t-C₄H₉)O]_(m)Zr[OSi(CH₂CH₃)₃]_(n), and [(t-C₄H₉)O]_(m)Hf[OSi(CH₂CH₃)₃]_(n). The value of m and n will be greater than 0 and less than 4 and m plus n is equal to 4 in these mixtures.

Chemical vapor deposition of the complexes to form thin metal silicate films, e.g., Zr and Hf silicate films with definite Zr:Si and Hf:Si ratios based upon the empirical formula may be accomplished by bringing the source into contact with a substrate as a liquid or in the vapor phase with a heated substrate (100–700° C.). Silicon wafers are the substrate of choice. Other methods of deposition include ALCVD, MBE, spin-on and misted vapor deposition.

The following examples are provided to illustrate various and preferred embodiments of the invention and are not intended to restrict the scope thereof.

EXAMPLE 1 Synthesis of a Precursor Having the Empirical Composition Hf(NEt₂)_(3.15)(OSiEt₃)_(0.85)

The synthesis of a precursor having the empirical composition Hf(NEt₂)_(3.15)(OSiEt₃)_(0.85) is achieved by the following process All manipulations were carried out in the absence of moisture and air under nitrogen or argon using standard Schlenk and glovebox techniques. In the glovebox, Hf(NEt₂)₄(75.71 g, 162.3 mmol) was weighed into a 500 mL Schlenk flask equipped with a stir bar. Hexane (˜200 mL) was added to the flask. A pressure-equalizing addition funnel containing HOSiEt₃ (21.3 g, 161 mmol) and hexane (˜50 mL) was attached to the flask and capped with a septum. The reaction apparatus was removed from the glovebox and attached to a Schlenk line.

Prior to introduction of reactants, the reaction flask was placed in a dry ice/isopropanol bath. A silanol solution was added dropwise to the reaction mixture over a period of 30 to 45 minutes. Stirring was continued overnight as the flask and bath were allowed to warm to room temperature to complete the reaction.

After completion of the reaction, the addition funnel was removed and replaced with a septum. The solvent was then removed under vacuum over a period of about 5 hours. The resulting liquid was vacuum distilled to yield 57 g of a single source precursor having the empirical composition Hf(NEt₂)_(3.15)(OSiEt₃)_(0.85) leading to an Hf/Si ratio of 3.7 by NMR spectrometry as a light yellow liquid. The precursor was characterized by ¹H and ¹³C NMR and by GC-MS. Both Hf(NEt₂)₄(m/z 468) and Hf(NEt₂)₃(OSiEt₃) (m/z 527) were detected by GC-MS. ¹H NMR was used to establish the empirical composition since the decomposition products diethylamine and hexaethyldisiloxane were both detected by GC-MS, indicating some decomposition on the column. The ¹³C NMR spectrum indicates the presence Hf(NEt₂)₄, Hf(NEt₂)₃(OSiEt₃), and Hf(NEt₂)₂(OSiEt₃)₂ as well.

EXAMPLE 2 Synthesis of a Precursor Having the Empirical Composition Hf(NEt₂)_(1.66)(OSiE₃)_(2.34)

The synthesis of a precursor having the empirical composition Hf(NEt₂)_(1.66)(OSiEt₃)_(2.34) was achieved by the following process. All manipulations were carried out in the absence of moisture and air under nitrogen or argon using standard Schlenk and glovebox techniques. In the glovebox, Hf(NEt₂)₄(74.96 g, 160.7 mmol) was weighed into a 500 mL Schlenk flask equipped with a stir bar. Hexane (˜100 mL) was added to the flask. A pressure-equalizing addition funnel containing HOSiEt₃(47.5 g, 359 mmol) and hexane (˜50 mL) was attached to the flask and capped with a glass stopper. The reaction apparatus was removed from the glovebox and attached to a Schlenk line.

While cooling the reaction flask in a dry ice/isopropanol bath the silanol solution was added dropwise to the reaction mixture over a period of about 15 minutes. Stirring was continued overnight as the flask and bath were allowed to warm to room temperature. The addition funnel was removed and replaced with a septum. The solvent was then removed under vacuum over a period of about 8 hours. The resulting liquid was vacuum distilled to yield 63 g of a precursor having the empirical composition Hf(NEt₂)_(1.66)(OSiEt₃)_(2.34) leading to an Hf/Si ratio of ˜0.70 by NMR spectrometry as a light orange liquid. The precursor was characterized by ¹H and ¹³C NMR. Integration of the ¹H NMR spectrum was used to establish the empirical composition. The ¹³C NMR spectrum indicates the presence Hf(NEt₂)₃(OSiEt₃), Hf(NEt₂)₂(OSiEt₃)₂, and Hf(NEt₂) (OSiEt₃)₃ as well.

EXAMPLE 2 Synthesis of a Precursor Having the Empirical Composition Hf(OtBu)_(3.30)(OSiEt₃)_(0.70)

The synthesis of a precursor having the empirical composition Hf(OtBu)_(3.30)(OSiEt₃)_(0.70) (an Hf/Si ratio of ˜4.7 was effected by the following process. All manipulations were carried out in the absence of moisture and air under nitrogen or argon using standard Schlenk and glovebox techniques. In the glovebox, Hf(OtBu)₄ (81.80 g, 173.7 mmol) was weighed into a 500 mL Schlenk flask equipped with a stir bar. Hexane (˜200 mL) was added to the flask. A pressure-equalizing addition funnel containing HOSiEt₃(23.01 g, 173.9 mmol) and hexane (˜10 mL) was attached to the flask and capped with a glass stopper. The reaction apparatus was removed from the glovebox and attached to a Schlenk line.

While cooling the reaction flask in a dry ice/isopropanol bath the silanol solution was added dropwise to the reaction mixture over a period of about 50 minutes. Stirring was continued overnight as the flask and bath were allowed to warm to room temperature. The addition funnel was removed and replaced with a septum. The solvent was then removed under vacuum over a period of about 10 hours. The resulting yellow cloudy liquid was vacuum distilled to yield 73.45 g of a precursor having the empirical composition Hf(OtBu)_(3.30)(OSiEt₃)_(0.70) by NMR spectrometry as a clear colorless liquid. The precursor was characterized by ¹H and ¹³C NMR. Integration of the ¹H NMR spectrum was used to establish the empirical composition. NMR spectra indicate the presence of both Hf(OtBu)₄ and Hf(OtBu)₃(OSiEt₃)₁.

EXAMPLE 4 Chemical Vapor Deposition of Hf Silicate Films

Chemical vapor deposition of Hf silicate films from a precursor having the empirical composition Hf(NEt₂)_(1.66)(OSiEt₃)_(2.34). The liquid precursor was transported via liquid delivery to a vaporizer and delivered to a CVD reaction chamber. The precursor was reacted at a heated substrate (200–800° C.) in a oxidizing environment to produce Hf silicate films. Si/Hf ratios based upon the empirical formula of the complex were between 0.62 and 0.71 in the resulting films as determined by RBS. The Si/Hf ratios were relatively insensitive to deposition temperature.

The chart in the FIGURE shows that the Si:Hf mole ratio in the resultant film does not vary significantly with temperature. Thus, differences in heating across a wafer will not result in compositional gradients across the wafer, which is critical to ensure device performance. As the semiconductor industry trends toward larger substrate sizes this advantage becomes even more pronounced over the use of physical mixtures of disparate compounds as precursors.

The present invention has been set forth with regard to several preferred embodiments, but the scope of the present invention should be ascertained from the claims which follow. 

1. A metal siloxide precursor which is composed of a complex represented by the empirical formula: (R)_(m)M—(O—SiR₁R₂R₃)_(n) wherein M is a Group 4 metal selected from the group consisting of zirconium and hafnium; R is (CH₃CH₂)₂N and R₁ R₂ and R₃ are ethyl; and m plus n is equal to a valence of the M metal (v).
 2. A metal siloxide or silyl-amide precursor which are composed of complexes represented by the empirical formulas: (R)_(m)M—(O—SiR₁R₂R₃)_(n) and (R)_(m)M—[N—(SiR₁R₂R₃)_(y)(R₄)_(2-y)]_(n) wherein M is a metal selected from the group consisting of Sc, Y, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; R₁ R₂ R₃ and R₄ are monodentate or polydentate ligands selected from the group consisting of C₁₋₈ alkyl, C₁₋₈ alkoxides, benzyl, ethers, halides, hydrides, amides, imides, azides, nitrates, cyclopentadienyls, carbonyls, a β-diketonate, and N(R₅)₂ wherein R₅ has the same meaning as R₁ R₂ R₃ and R₄ and their fluorine, oxygen and nitrogen substituted analogs; R is a monodentate or polydentate ligand selected from the group consisting of C₁₋₈ alkyl, C₁₋₈ alkoxides, benzyl, halides, hydrides, amides, azides, nitrates, cyclopentadienyls, a β-diketonate, and N(R₅)₂ wherein R₅ has the same meaning as R₁ R₂ R₃ and R₄ and their fluorine, oxygen and nitrogen substituted analogs, m and n are positive numbers and m plus n is equal to the valence of the M metal (v), and y is either 1 or
 2. 3. The metal siloxide or silyl-amide precursor complex of claim 2 wherein the β-ketonate is derived from 2,4-pentanedione, and 2,2,6,6-tetramethylheptane-3,5-dione.
 4. The metal siloxide or silyl-amide precursor complex of claim 2 wherein R, R₁ R₂ R₃ and R₄ are selected from methyl, ethyl, i-propyl and t-butyl; methyl ether, diethyl ether, phenyl ether; methoxy, ethoxy, propoxy, i-butoxy, s-butoxy, and t-butoxy, dimethylamido, and diethylamido.
 5. A metal silyl-amide precursor complex which is represented by the formula: (R)_(m)M—[N—(SiR₁R₂R₃)_(y)(R₄)_(2-y)]_(n) wherein M is selected from the group consisting of hafnium and zirconium, R is t-butoxy or diethylamido or dimethylamido, and R₁ R₂ R₃ and R₄ are methyl or ethyl; and m plus n is equal to the valence of the metal (v) and y is either 1 or
 2. 6. A process for producing a metal siloxide precursor complex which is represented by the empirical formula: (R)_(m)M—(O—SiR₁R₂R₃)_(n) wherein M is a metal selected from the group consisting of hafnium and zirconium; R t-butoxy, diethylamido, or dimethylamido and R₁, R₂, and R₃ are ethyl; and m plus n is equal to the valence of the metal (v), which comprises the step: (a) reacting a metal complex of the formula M(R)₄ has the meaning recited above with a silanol of the formula HO—Si—R₁ R₂ R₃ wherein R₁R₂ and R₃ have the meanings recited above.
 7. A metal siloxide precursor mixture of the formula Hf(O-t-Bu)_(m)(OSiEt₃)_(n) where m and n are positive numbers and m plus n is equal to four and hafnium is in the +4 oxidation state.
 8. A metal siloxide precursor mixture of the formula Hf(NEt₂)_(m)(OSiEt₃)_(n) where m and n are positive numbers and m plus n is equal to four and hafnium is in the +4 oxidation state.
 9. A metal siloxide precursor which comprising a complex represented by the empirical formula: (R)_(m)M—(O—SiR₁R₂R₃)_(n) wherein M is a metal having a valence number v and selected from the group consisting of Zr, Hf, Sc, Y, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; R₁, R₂, R₃, and R₄ are each independently monodentate or polydentate ligands selected from the group consisting of C₁₋₈ alkyl, C₁₋₈ alkoxide benzyl, hydrides, amides, azides, nitrates, cyclopentadienyls, and N(R₅)₂ wherein R₅ has the same meaning as R₁, R₂, R₃ and R₄ and their fluorine, oxygen and nitrogen substituted analogs; R is a monodentate or polydentate ligand selected from the group consisting of, hydrides, amides, azides, nitrates, cyclopentadienyls, and N(R₅)₂ wherein R₅ has the same meaning as R₁, R₂, R₃ and R₄ and their fluorine, oxygen and nitrogen substituted analogs; and m and n are positive numbers wherein m+n=v.
 10. The precursor of claim 9 wherein M is selected from zirconium and hafnium.
 11. The precursor of claim 10 wherein R₁ R₂ and R₃ are methyl or ethyl.
 12. The precursor of claim 11 wherein R is t-butoxy and R₁ R₂ and R₃ are ethyl.
 13. A process for preparing a metal siloxide precursor complex which is represented by the empirical formula: (R)_(m)M—(O—SiR₁R₂R₃)_(n) wherein M is a metal having a valence number v and selected from Zr, Hf, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; R₁, R₂, and R₃, and R₄ are each independently monodentate or polydentate ligands selected from C₁₋₈ alkyl, C₁₋₈ alkoxides, benzyl, halides, hydrides, amides, azides, nitrates, cyclopentadienyls, and N(R₅)₂ wherein R₅ has the same meaning as R₁, R₂, R₃ and R₄ and their fluorine, oxygen and nitrogen substituted analogs; R is a monodentate or polydentate ligand selected from hydrides, amides, azides, nitrates, cyclopentadienyls and N(R₅)₂ wherein R₅ has the same meaning as R₁, R₂, R₃ and R₄ and their fluorine, oxygen and nitrogen substituted analogs; and m and n are positive numbers wherein m+n=v, the process comprising: reacting a metal complex of the formula M(OR)₄ where R has the meaning recited above with a silanol of the formula HO—Si—R₁ R₂ R₃ wherein R₁ R₂ and R₃ have the meanings recited above.
 14. A process for preparing a metal silyl-amide precursor which is represented by the empirical formula: (R)_(m)M—[N—(SiR₁R₂R₃)_(y)(R₄)_(2-y)]_(n) wherein M is a metal having a valence number v and selected from the group consisting of Zr, Hf, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; R₁, R₂, R₃, and R₄ are each independently monodentate or polydentate ligands selected from the group consisting of C₁₋₈ alkyl, C₁₋₈ alkoxides, benzyl, halides, hydrides, amides, azides, nitrates, cyclopentadienyls, a β-diketonate, and N(R₅)₂ wherein R₅ has the same meaning as R₁, R₂, R₃ and R₄ and their fluorine, oxygen and nitrogen substituted analogs; R is a monodentate or polydentate ligand comprising C₁₋₈ alkoxides; y is either 1 or 2; and m and n are positive numbers wherein m+n=v, the process comprising: reacting a metal complex of the formula M(R)₄ where R has the meaning recited above with a silyl amine having the formula HN(Si R₁ R₂ R₃)₂, H₂N(Si R₁ R₂ R₃), or HNR₄(SiR₁ R₂ R₃) wherein R₁, R₂, R₃, and R₄ have the meanings recited above.
 15. A metal silyl-amide precursor which is composed of a complex represented by the empirical formula: (R)_(m)M—[N—(SiR₁R₂R₃)_(y)(R₄)_(2-y)]_(n) wherein M is a metal having a valence number v and selected from Zr, Hf, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu; R₁, R₂, R₃, and R₄ are each independently monodentate or polydentate ligands selected from C₁₋₈ alkyl, C₁₋₈ alkoxides, benzyl, halides, hydrides, amides, azides, nitrates, cyclopentadienyls, a β-diketonate, and N(R₅)₂ wherein R₅ has the same meaning as R₁, R₂, R₃ and R₄ and their fluorine, oxygen and nitrogen substituted analogs; R is a monodentate or polydentate ligand selected from C₁₋₈ alkoxides, hydrides, amides, azides, nitrates, a β-diketonate, and N(R₅)₂ wherein R₅ has the same meaning as R₁, R₂, R₃ and R₄ and their fluorine, oxygen and nitrogen substituted analogs; y is either 1 or 2; and m and n are positive numbers wherein m+n=v. 